Search results for: glycerol carbonate

Authors: Satyendra P. Chaurasia, Aditi Sharma, Ajay K. Dalai

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The esterification of Docosahexaenoic acid (DHA) with glycerol using immobilized Mucor mie-hei lipase (MML) and Rhizopus oryzae lipase (ROL) have been studied in the present paper to synthesize triglycerides (TG) rich in DHA. Both immobilized lipases (MML and ROL), and their support materials (immobead-150 and ion-exchange resin) were characterized and compared for surface properties with BET, for chemical functional groups with FT-IR, and for particle size distribution with particle size analyzer. The most suitable reaction conditions for synthesis of DHA rich TG in biphasic solvent system were found as 1:3 (wt/wt) glycerol to DHA ratio, 1:1 (wt/wt) buffer to DHA ratio, 1:1 (wt/wt) solvent to DHA ratio at 50 ºC temperature, and 600 rpm speed of agitation with 100 mg of immobilized lipases. Maximum 95.9 % esterification was obtained with immobilized MML in 14 days reaction with formation of 65.7 wt% DHA rich TG. Whereas, immobilized ROL has shown formation of only 23.8 wt% DHA rich TG with total 78.9 % esterification in 15 days. Additionally, repeated use of both immobilized lipases was con-ducted up to five cycles, indicated 50.4% and 41.2 % activity retention after fifth repeated use of immobilized MML and ROL, respectively.

Keywords: DHA, immobilized Mucor miehei lipase, Rhizopus oryzae lipase, esterification

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Authors: María José Carrero, Ana M. Borreguero, Juan F. Rodríguez, María M. Velencoso, Ángel Serrano, María Jesús Ramos

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Flame-retardants are incorporated in different materials in order to reduce the risk of fire, either by providing increased resistance to ignition, or by acting to slow down combustion and thereby delay the spread of flames. In this work, polyether polyols with fire retardant properties were synthesized due to their wide application in the polyurethanes formulation. The combustion of polyurethanes is primarily dependent on the thermal properties of the polymer, the presence of impurities and formulation residue in the polymer as well as the supply of oxygen. There are many types of flame retardants, most of them are phosphorous compounds of different nature and functionality. The addition of these compounds is the most common method for the incorporation of flame retardant properties. The employment of glycerol phosphate sodium salt as initiator for the polyol synthesis allows obtaining polyols with phosphate groups in their structure. However, some of the critical points of the use of glycerol phosphate salt are: the lower reactivity of the salt and the necessity of a solvent (dimethyl sulfoxide, DMSO). Thus, the main aim in the present work was to determine the amount of the solvent needed to get a good solubility of the initiator salt. Although the anionic polymerization mechanism of polyether formation is well known, it seems convenient to clarify the role that DMSO plays at the starting point of the polymerization process. Regarding the fact that the catalyst deprotonizes the hydroxyl groups of the initiator and as a result of this, two water molecules and glycerol phosphate alkoxide are formed. This alkoxide, together with DMSO, has to form a homogeneous mixture where the initiator (solid) and the propylene oxide (PO) are soluble enough to mutually interact. The addition rate of PO increased when the solvent/initiator ratios studied were increased, observing that it also made the initiation step shorter. Furthermore, the molecular weight of the polyol decreased when higher solvent/initiator ratios were used, what revealed that more amount of salt was activated, initiating more chains of lower length but allowing to react more phosphate molecules and to increase the percentage of phosphorous in the final polyol. However, the final phosphorous content was lower than the theoretical one because only a percentage of salt was activated. On the other hand, glycerol phosphate disodium salt was still partially insoluble in DMSO studied proportions, thus, the recovery and reuse of this part of the salt for the synthesis of new flame retardant polyols was evaluated. In the recovered salt case, the rate of addition of PO remained the same than in the commercial salt but a shorter induction period was observed, this is because the recovered salt presents a higher amount of deprotonated hydroxyl groups. Besides, according to molecular weight, polydispersity index, FT-IR spectrum and thermal stability, there were no differences between both synthesized polyols. Thus, it is possible to use the recovered glycerol phosphate disodium salt in the same way that the commercial one.

Keywords: DMSO, fire retardants, glycerol phosphate disodium salt, recovered initiator, solvent

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Authors: Jong-Ho Moon, Dong-Ho Lee, Hyunuk Kim, Young Cheol Park, Jong-Seop Lee, Jae-deok Jeon, Hyung-Keun Lee

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A novel membrane reactor process for DMC synthesis from carbon dioxide has been developing in Korea Institute of Energy Research. The scheme of direct synthesis of DMC from CO₂ and Methanol is 'CO₂ + 2MeOH ↔ DMC + H₂O'. Among them, reactants are CO₂ and MeOH, product is DMC, and byproduct is H₂O (water). According to Le Chatelier’s principle, removing byproduct (water) can shift the reaction equilibrium to the right (DMC production). The main purpose of this process is removing water during the reaction. For efficient in situ water removal (dehydration) and DMC separation, zeolite 4A membranes with very small pore diameter and hydrophilicity were introduced. In this study, pervaporation performances of binary and ternary DMC / methanol / water mixtures were evaluated.

Keywords: dimehtyl carbonate, methanol, water, zeolite membrane, pervaporation

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Authors: Olfat A. Mohamed

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Rhamnolipids biosurfactants have distinct properties given them importance in many industrial applications, especially their great new future applications in cosmetic and pharmaceutical industries. These applications have encouraged the search for diverse and renewable resources to control the cost of production. The experimental results were then applied to find a suitable mathematical model for obtaining the design criteria of the batch bioreactor. This research aims to produce Rhamnolipids from different oily wastewater sources such as petroleum crude oil (PO) and vegetable oil (VO) by using Pseudomonas aeruginosa ATCC 9027. Different concentrations of the PO and the VO are added to the media broth separately are in arrangement (0.5 1, 1.5, 2, 2.5 % v/v) and (2, 4, 6, 8 and 10%v/v). The effect of the initial concentration of oil residues and the addition of glycerol and palmitic acid was investigated as an inducer in the production of rhamnolipid and the surface tension of the broth. It was found that 2% of the waste (PO) and 6% of the waste (VO) was the best initial substrate concentration for the production of rhamnolipids (2.71, 5.01 g rhamnolipid/l) as arrangement. Addition of glycerol (10-20% v glycerol/v PO) to the 2% PO fermentation broth led to increase the rhamnolipid production (about 1.8-2 times fold). However, the addition of palmitic acid (5 and 10 g/l) to fermentation broth contained 6% VO rarely enhanced the production rate. The experimental data for 2% initially (PO) was used to estimate the various kinetic parameters. The following results were obtained, maximum rate or velocity of reaction (Vmax) = 0.06417 g/l.hr), yield of cell weight per unit weight of substrate utilized (Yx/s = 0.324 g Cx/g Cs) maximum specific growth rate (μmax = 0.05791 hr⁻¹), yield of rhamnolipid weight per unit weight of substrate utilized (Yp/s)=0.2571gCp/g Cs), maintenance coefficient (Ms =0.002419), Michaelis-Menten constant, (Km=6.1237 gmol/l), endogenous decay coefficient (Kd=0.002375 hr⁻¹). Predictive parameters and advanced mathematical models were applied to evaluate the time of the batch bioreactor. The results were as follows: 123.37, 129 and 139.3 hours in respect of microbial biomass, substrate and product concentration, respectively compared with experimental batch time of 120 hours in all cases. The expected mathematical models are compatible with the laboratory results and can, therefore, be considered as tools for expressing the actual system.

Keywords: batch bioreactor design, glycerol, kinetic parameters, petroleum crude oil, Pseudomonas aeruginosa, rhamnolipids biosurfactants, vegetable oil

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Authors: Almas Rajguru, Archana Kamath, Rachana Singh

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The study aims to determine the depositional facies, high-resolution sequence stratigraphy, and diagenetic processes of Early Oligocene carbonates in N & N-W of Heera, Mumbai Offshore. Foraminiferal assemblage and microfacies from cores of Well A, B, C, D and E are indicative of facies association related to four depositional environments, i.e., restricted inner lagoons-tidal flats, shallow open lagoons, high energy carbonate bars-shoal complex and deeper mid-ramps of a westerly dipping homoclinal carbonate ramp. Two high-frequency (4th Order) depositional sequences bounded by sequence boundary, DS1 and DS2, displaying hierarchical stacking patterns, are identified and correlated across wells. Vadose zone diagenesis effect during short diastem/ subaerial exposure has rendered good porosity due to dissolution in HST carbonates and occasionally affected underlying TST sediments (Well D, C and E). On mapping and correlating the sequences, the presence of thin carbonate bars that can be potential reservoirs are envisaged along NW-SE direction, towards north and south of Wells E, D and C. A more pronounced development of these bars in the same orientation can be anticipated towards the west of the study area.

Keywords: sequence stratigraphy, depositional facies, diagenesis petrography, early Oligocene, Mumbai offshore

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Authors: Basem A. El Werfallia, Osama R. Shaltamiab, Ragab M. Al Alwanyc

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The present work aims to characterize the geochemistry of the beach sands along the Mediterranean Coast from Al Kuwifia to Tolmeita, NE Libya. The major oxides CaO and MgO are the main constituents of the carbonate minerals; calcite and aragonite. SiO2 is mainly in the form of quartz. Sometimes a high quotient of SiO2 together with the oxides; Al2O3, K2O and partly of Na2O, TiO2 and Fe2O3 are essentially allocated within the structure of the feldspars. Part of Na2O and the content of Cl belong mainly to halite. Part of Fe2O3 and TiO2 may be accommodated as iron oxyhydroxides. Part of CaO and the content of SO3 are allotted within the gypsum structure. Ba, Sr, Th, U and REE are basicallycontrolled by the carbonate fraction, while Cu, Zn, V and Cr are strongly correlated with Al2O3.

Keywords: geochemistry, major oxides, Al Kuwifia, Tolmeita

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Authors: Hammad T. Janjuhah, Josep Sanjuan, Mohamed K. Salah

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Biological and chemical activities in carbonates are responsible for the complexity of the pore system. Primary porosity is generally of natural origin while secondary porosity is subject to chemical reactivity through diagenetic processes. To understand the integrated part of hydrocarbon exploration, it is necessary to understand the carbonate pore system. However, the current porosity classification scheme is limited to adequately predict the petrophysical properties of different reservoirs having various origins and depositional environments. Rock classification provides a descriptive method for explaining the lithofacies but makes no significant contribution to the application of porosity and permeability (poro-perm) correlation. The Central Luconia carbonate system (Malaysia) represents a good example of pore complexity (in terms of nature and origin) mainly related to diagenetic processes which have altered the original reservoir. For quantitative analysis, 32 high-resolution images of each thin section were taken using transmitted light microscopy. The quantification of grains, matrix, cement, and macroporosity (pore types) was achieved using a petrographic analysis of thin sections and FESEM images. The point counting technique was used to estimate the amount of macroporosity from thin section, which was then subtracted from the total porosity to derive the microporosity. The quantitative observation of thin sections revealed that the mouldic porosity (macroporosity) is the dominant porosity type present, whereas the microporosity seems to correspond to a sum of 40 to 50% of the total porosity. It has been proven that these Miocene carbonates contain a significant amount of microporosity, which significantly complicates the estimation and production of hydrocarbons. Neglecting its impact can increase uncertainty about estimating hydrocarbon reserves. Due to the diversity of geological parameters, the application of existing porosity classifications does not allow a better understanding of the poro-perm relationship. However, the classification can be improved by including the pore types and pore structures where they can be divided into macro- and microporosity. Such studies of microporosity identification/classification represent now a major concern in limestone reservoirs around the world.

Keywords: overview of porosity classification, reservoir characterization, microporosity, carbonate reservoir

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Authors: Basem A. El Werfalli, Osama R. Shaltamiab, Ragab M. Al Alwany

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The present work aims to characterize the geochemistry of the beach sands along the Mediterranean Coast from Al Kuwifia to Tolmeita, NE Libya. The major oxides CaO and MgO are the main constituents of the carbonate minerals; calcite and aragonite. SiO₂ is mainly in the form of quartz. Sometimes a high quotient of SiO₂ together with the oxides; Al₂O₃, K₂O and partly of Na₂O, TiO₂ and Fe₂O₃ are essentially allocated within the structure of the feldspars. Part of Na₂O and the content of Cl belong mainly to halite. Part of Fe₂O₃ and TiO₂ may be accommodated as iron oxyhydroxides. Part of CaO and the content of SO₃ are allotted within the gypsum structure. Ba, Sr, Th, U and REE are basically controlled by the carbonate fraction, while Cu, Zn, V and Cr are strongly correlated with Al₂O₃.

Keywords: geochemistry, major oxides, Al Kuwifia, Tolmeita

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Authors: Adrien Cornille, Marine Blain, Bernard Boutevin, Sylvain Caillol

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Generally, linear polyurethanes (PUs) are obtained by the reaction between an oligomeric diol, a short diol as chain extender and a diisocyanate. However the use of diisocyanate should be avoided since they are generally very harmful for human health. Therefore the synthesis of NIPUs (non isocyanate PUs) from step growth polymerization of dicyclocarbonates and diamines should be favoured. This method is particularly interesting since no hazardous isocyanates are used. Thus, this reaction, extensively studied by Endo et al. is currently gaining a lot of attention as a substitution route for the synthesis of NIPUs, both from industrial and academic community. However, the reactivity of reaction between amine and cyclic carbonate is a major scientific issue, since cyclic carbonates are poorly reactive. Thus, our team developed several synthetic ways for the synthesis of various di-cyclic carbonates based on C5-, C6- and dithio- cyclic carbonates, from different biobased raw materials (glycerin isosorbide, vegetable oils…). These monomers were used to synthesize NIPUs with various mechanical and thermal properties for various applications. We studied the reactivity of reaction with various catalysts and find optimized conditions for room temperature reaction. We also studied the radical copolymerization of cyclic carbonate monomers in styrene-acrylate copolymers for coating applications. We also succeeded in the elaboration of biobased NIPU flexible foams. To the best of our knowledge, there is no report in literature on the preparation of non-isocyanate polyurethane foams.

Keywords: foam, nonisocyanate polyurethane, cyclic carbonate, blowing agent, scanning electron microscopy

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Authors: Jessica Vasil'chuk, Elena Ivanova, Pavel Krechetov, Vladimir Litvinsky, Nadine Budantseva, Julia Chizhova, Yurij Vasil'chuk

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Carbonate minerals’ isotopic composition is widely used as a proxy for environmental parameters of the past. Pedogenic carbonate coatings on lower surfaces of coarse rock fragments are studied in order to indicate the climatic conditions and predominant vegetation under which they were formed. The purpose of the research is to characterize the isotopic composition of carbonate pedofeatures in soils of Minusink Hollow and estimate its correlation with isotopic composition of soil pore water, precipitation, vegetation and parent material. The samples of pedogenic carbonates, vegetation, carbonate parent material, soil water and precipitation water were analyzed using the Delta-V mass spectrometer with options of a gas bench and element analyser. The soils we studied are mainly Kastanozems that are poorly moisturized, therefore soil pore water was extracted by ethanol. Oxygen and carbon isotopic composition of pedogenic carbonates was analyzed in 3 key sites. Kazanovka Khakass state national reserve, Hankul salt lake, region of Sayanogorsk aluminum smelter. Vegetation photosynthetic pathway in the region is mainly C3. δ18O values of carbonate coatings in soils of Kazanovka vary in a range from −7.49 to −10.5‰ (vs V-PDB), and the smallest value −13.9‰ corresponds the coatings found between two buried soil horizons which 14C dates are 4.6 and 5.2 kyr BP. That may indicate cooler conditions of late Holocene than nowadays. In Sayanogorsk carbonates’ δ18O range is from −8.3 to −11.1‰ and near the Hankul Lake is from −9.0 to −10.2‰ all ranges are quite similar and may indicate coatings’ uniform formation conditions. δ13C values of carbonate coatings in Kazanovka vary from −2.5 to −6.7‰, the highest values correspond to the soils of Askiz and Syglygkug rivers former floodplains. For Sayanogorsk the range is from −4.9 to −6.8‰ and for Hankul from −2.3 to −5.7‰, where the highest value is for the modern salt crust. δ13C values of coatings strongly decrease from inner (older) to outer (younger) layers of coatings, that can indicate differences connected with the diffusion of organic material. Carbonate parent material δ18O value in the region vary from −11.1 to −12.0‰ and δ13C values vary from −4.9 to −5.7‰. Soil pore water δ18O values that determine the oxygen isotope composition of carbonates vary due to the processes of transpiration and mixing in the studied sites in a wide range of −2.0 to −13.5‰ (vs V-SMOW). Precipitation waters show δ18O values from -6.6‰ in May and -19.0‰ in January (snow) due to the temperature difference. The main conclusions are as follows: pedogenic carbonates δ13C values (−7…−2,5‰) show no correlation with modern C3 vegetation δ13C values (−30…−26‰), expected values under such vegetation are (−19…−15‰) but are closer to C4 vegetation. Late Holocene climate for the Minusinsk Hollow according to obtained data on isotope composition of carbonates and soil pore water chemical composition was dryer and cooler than present, that does not contradict with paleocarpology data obtained for the region. The research was supported by Russian Science Foundation (grant №14-27-00083).

Keywords: carbon, oxygen, pedogenic carbonates, South Siberia, stable isotopes

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Authors: Kianoosh Shojae

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In recent years, the environmental challenges due to the excessive use of fossil fuels have led to heightened greenhouse gas production. In response, biodiesel has emerged as a cleaner alternative, offering reduced pollutant emissions compared to traditional fuels. The large-scale production of biodiesel, involving ester exchange of animal fats or vegetable oils, results in a surplus of crude glycerin. With environmental regulations on the rise and an increasing demand for biodiesel, glycerin production has seen a significant upswing. This paper focuses on the economic significance of glycerin through its pyrolysis as a raw material, particularly in the synthesis of metals. As industries pivoted towards cleaner fuels, glycerin, as a byproduct of biodiesel production, is poised to remain a cost-effective and surplus product. In this work, for evaluating the possible performance of using the gaseous products from the pyrolysis reaction of glycerol, we concerned the glycerin pyrolysis reactions, emphasizing the catalytic role of activated carbon, various reaction pathways and the impact of carrier gas flow rate on hydrogen production, providing valuable insights into the evolving landscape of sustainable fuel alternatives.

Keywords: biodiesel, glycerin pyrolysis, activated carbon catalysis, syngas

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Authors: Chongwain G. Mbzighaa, Christopher M. Agyingi, Josepha-Forba-Tendo

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Background and aim: Sedimentological, geochemical and petrographic studies were carried out on carbonate-bearing argillites outcropping at the southeastern flank of Mount Cameroon (Likomba) to determine the lithofacies and their associations, major element geochemistry and mineralogy. Methods: Major elements of the rocks were analyzed using XRF technique. Thermal analysis and thin section studies were carried out accompanied with the determination of insoluble components of the carbonates. Results: The carbonates are classed as biomicrites with siderite being the major carbonate mineral. Clay, quartz and pyrite constitute the major insoluble components of these rocks. Geochemical results depict a broad variation in their concentrations with silica and iron showing the highest concentrations and sodium and manganese with the least concentrations. Two factors were revealed with the following elemental associations, Fe2O3-MgO-Mn2O3 (72.56 %) and TiO2-SiO2-Al2O3-K2O (23.20%) indicating both Fe-enrichment, the subsequent formation of the siderite and the contribution of the sediments to the formation of these rocks. Conclusion: The rocks consist of cyclic iron-rich carbonates alternating with sideritic-shales and might have been formed as a result of variations in the sea conditions as well as variation in sediment influx resulting from transgression and regression sequences occurring in a shallow to slightly deep marine environments.

Keywords: sedimentology, geochemistry, petrography, iron carbonates, Likomba

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Authors: Rory Anthony Hutagalung, Leonardus Widjaja

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Microalgae Meyerella planktonica is a potential biofuel source because it can grow in bulk in either autotrophic or heterotrophic condition. However, the quantitative growth of this algal type is still low as it tends to precipitates on the bottom. Beside, the lipid concentration is still low when grown in autotrophic condition. In contrast, heterotrophic condition can enhance the lipid concentration. The combination of autotrophic condition and agitation treatment was conducted to increase the density of the culture. On the other hand, a heterotrophic condition was set up to raise the lipid production. A two-stage experiment was applied to increase the density at the first step and to increase the lipid concentration in the next step. The autotrophic condition resulted higher density but lower lipid concentration compared to heterotrophic one. The agitation treatment produced higher density in both autotrophic and heterotrophic conditions. The two-stage experiment managed to enhance the density during the autotrophic stage and the lipid concentration during the heterotrophic stage. The highest yield was performed by using 0.4% v/v glycerol as a carbon source (2.9±0.016 x 106 cells w/w) attained 7 days after the heterotrophic stage began. The lipid concentration was stable starting from day 7.

Keywords: agitation, glycerol, heterotrophic, lipid productivity, Meyerella planktonica

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Authors: Miloud M. Abugares

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This study concentrates on the facies analysis, cyclicity and depositional environment of the Upper Cretaceous (Cenomanian) carbonate ramp deposits of the Lidam Formation. Core description, petrographic analysis data from five wells in Hamid and 3V areas in the SE Sirt Basin, Libya were studied in detail. The Lidam Formation is one of the main oil producing carbonate reservoirs in Southeast Sirt Basin and this study represents one of the key detailed studies of this Formation. In this study, ten main facies have been identified. These facies are; Chicken-Wire Anhydrite Facies, Fine Replacive Dolomite Facies, Bioclastic Sandstone Facies, Laminated Shale Facies, Stromatolitic Laminated Mudstone Facies, Ostracod Bioturbated Wackestone Facies, Bioturbated Mollusc Packstone Facies, Foraminifera Bioclastic Packstone/Grainstone Facies Peloidal Ooidal Packstone/Grainstone Facies and Squamariacean/Coralline Algae Bindstone Facies. These deposits are inferred to have formed in supratidal sabkha, intertidal, semi-open restricted shallow lagoon and higher energy shallow shoal environments. The overall depositional setting is interpreted as have been deposited in inner carbonate ramp deposits. The best reservoir quality is encountered in Peloidal- Ooidal Packstone/Grainstone facies, these facies represents storm - dominated shoal to back shoal deposits and constitute the inner part of carbonate ramp deposits. The succession shows a conspicuous hierarchical cyclicity. Porous shoal and backshoal deposits form during maximum transgression system and early regression hemi-cycle of the Lidam Fm. However; oil producing from shoal and backshoal deposits which only occur in the upper intervals 15 - 20 feet, which forms the large scale transgressive cycle of the Upper Lidam Formation.

Keywords: Lidam Fm. Sirt Basin, Wackestone Facies, petrographic, intertidal

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Authors: Dongwoo Kang, Yunsung Yoo, Injun Kim, Jongin Lee, Jinwon Park

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Since industrial revolution, energy usage by human-beings has been drastically increased resulting in the enormous emissions of carbon dioxide into the atmosphere. High concentration of carbon dioxide is well recognized as the main reason for the climate change by breaking the heat equilibrium of the earth. In order to decrease the amount of carbon dioxide emission, lots of technologies have been developed. One of the methods is to capture carbon dioxide after combustion process using liquid type absorbents. However, for some nations, captured carbon dioxide cannot be treated and stored properly due to their geological structures. Also, captured carbon dioxide can be leaked out when crust activities are active. Hence, the method to convert carbon dioxide as stable and useful products were developed. It is usually called CCU, that is, Carbon Capture and Utilization. There are several ways to convert carbon dioxide into useful substances. For example, carbon dioxide can be converted and used as fuels such as diesel, plastics, and polymers. However, these types of technologies require lots of energy to make stable carbon dioxide into a reactive one. Hence, converting it into metal carbonates salts have been studied widely. When carbon dioxide is captured by alkanolamine-based liquid absorbents, it exists as ionic forms such as carbonate, carbamate, and bicarbonate. When adequate metal ions are added, metal carbonate salt can be produced by ionic reaction with fast reaction kinetics. However, finding metal sources can be one of the problems for this method to be commercialized. If natural resources such as calcium oxide were used to supply calcium ions, it is not thought to have the economic feasibility to use natural resources to treat carbon dioxide. In this research, high concentrated industrial wastewater produced from refined salt production facility have been used as metal supplying source, especially for calcium cations. To ensure purity of final products, calcium ions were selectively separated in the form of gypsum dihydrate. After that, carbon dioxide is captured using alkanolamine-based absorbents making carbon dioxide into reactive ionic form. And then, high purity calcium carbonate salt was produced. The existence of calcium carbonate was confirmed by X-Ray Diffraction (XRD) and Scanning Electron Microscopy (SEM) images. Also, carbon dioxide loading curves for absorption, conversion, and desorption were provided. Also, in order to investigate the possibility of the absorbent reuse, reabsorption experiments were performed either. Produced calcium carbonate as final products is seemed to have potential to be used in various industrial fields including cement and paper making industries and pharmaceutical engineering fields.

Keywords: alkanolamine, calcium carbonate, climate change, seawater, industrial wastewater

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Authors: P. Raajeswari, S. M. Devatha, R. Pragatheeswari

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The edible packaging is a new trendsetter in the era of modern packaging. The researchers and food scientist recognise edible packaging as a useful alternative or addition to conventional packaging to reduce waste and to create novel applications for improving product stability. Starch was extracted from different sources that contains abundantly like potato, tapioca, rice, wheat, and corn. The starch based edible films and cutleries are developed as an alternative for conventional packages providing the nutritional benefit when consumed along with the food. The development of starch based edible films by the extraction of starch from various raw ingredients at lab scale level. The films are developed by the employment of plasticiser at different concentrations of 1.5ml and 2ml. The films developed using glycerol as a plasticiser in filmogenic solution to increase the flexibility and plasticity of film. It reduces intra and intermolecular forces in starch, and it increases the mobility of starch based edible films. The films developed are tested for its functional properties such as thickness, tensile strength, elongation at break, moisture permeability, moisture content, and puncture strength. The cutleries like spoons and cups are prepared by making dough and rolling the starch along with water. The overall results showed that starch based edible films absorbed less moisture, and they also contributed to the low moisture permeability with high tensile strength. Food colorants extracted from red onion peel, pumpkin, and red amaranth adds on the nutritive value, colour, and attraction when incorporated in edible cutleries, and it doesn’t influence the functional properties. Addition of a low quantity of glycerol in edible films and colour extraction from onion peel, pumpkin, and red amaranth enhances biodegradability and provides a good quantity of nutrients when consumed. Therefore, due to its multiple advantages, food starch can serve as the best response for eco-friendly industrial products aimed to replace single use plastics at low cost.

Keywords: edible films, edible cutleries, plasticizer, glycerol, starch, functional property

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Authors: Rangrong Yoksan, Amporn Sane, Nattaporn Khanoonkon, Chanakorn Yokesahachart, Narumol Noivoil, Khanh Minh Dang

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Polylactic acid (PLA) is the most commercially available bio-based and biodegradable plastic at present. PLA has been used in plastic related industries including single-used containers, disposable and environmentally friendly packaging owing to its renewability, compostability, biodegradability, and safety. Although PLA demonstrates reasonably good optical, physical, mechanical, and barrier properties comparable to the existing petroleum-based plastics, its brittleness and mold shrinkage as well as its price are the points to be concerned for the production of rigid and semi-rigid packaging. Blending PLA with other bio-based polymers including thermoplastic starch (TPS) is an alternative not only to achieve a complete bio-based plastic, but also to reduce the brittleness, shrinkage during molding and production cost of the PLA-based products. TPS is a material produced mainly from starch which is cheap, renewable, biodegradable, compostable, and non-toxic. It is commonly prepared by a plasticization of starch under applying heat and shear force. Although glycerol has been reported as one of the most plasticizers used for preparing TPS, its migration caused the surface stickiness of the TPS products. In some cases, mixed plasticizers or natural fibers have been applied to impede the retrogradation of starch or reduce the migration of glycerol. The introduction of fibers into TPS-based materials could reinforce the polymer matrix as well. Therefore, the objective of the present research is to study the effect of starch type (i.e. native starch and phosphate starch), plasticizer type (i.e. glycerol and xylitol with a weight ratio of glycerol to xylitol of 100:0, 75:25, 50:50, 25:75, and 0:100), and fiber content (i.e. in the range of 1-25 % wt) on properties of PLA/TPS blend and composite. PLA/TPS blends and composites were prepared using a twin-screw extruder and then converted into dumbbell-shaped specimens using an injection molding machine. The PLA/TPS blends prepared by using phosphate starch showed higher tensile strength and stiffness than the blends prepared by using the native one. In contrast, the blends from native starch exhibited higher extensibility and heat distortion temperature (HDT) than those from the modified starch. Increasing xylitol content resulted in enhanced tensile strength, stiffness, and water resistance, but decreased extensibility and HDT of the PLA/TPS blend. Tensile properties and hydrophobicity of the blend could be improved by incorporating silane treated-jute fibers.

Keywords: polylactic acid, thermoplastic starch, Jute fiber, composite, blend

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Authors: Wei-Bo Hua, Zhuo Zheng, Xiao-Dong Guo, Ben-He Zhong

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The layered structure LiNi1/3Co1/3Mn1/3-xAlxO2 (x = 0 ~ 0.04) series cathode materials were synthesized by a carbonate co-precipitation method, followed by a high temperature calcination process. The influence of Al substitution on the microstructure and electrochemical performances of the prepared materials was investigated by X-Ray diffraction (XRD), scanning electron microscopy (SEM), and galvanostatic charge/discharge test. The results show that the LiNi1/3Co1/3Mn1/3-xAlxO2 has a well-ordered hexagonal "α" -NaFeO2 structure. Although the discharge capacity of Al-doped samples decreases as x increases, LiNi1/3Co1/3Mn1/3-0.02Al0.02O2 exhibits superior capacity retention at high voltage (4.6 V). Therefore, LiNi1/3Co1/3Mn1/3-0.02Al0.02O2 is a promising material for “green” vehicles.

Keywords: lithium ion battery, carbonate co-precipitation, doping, microstructure, electrochemical properties

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Authors: Peter Thissen

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In this work, we report about the influence of the chemical potential of water on the carbonation reaction of wollastonite (CaSiO3) as model surface of cement and concrete. Total energy calculations based on density functional theory (DFT) combined with kinetic barrier predictions based on nudge elastic band (NEB) method show that the exposure of the water-free wollastonite surface to CO2 results in a barrier-less carbonation. CO2 reacts with the surface oxygen and forms carbonate (CO32-) complexes together with a major reconstruction of the surface. The reaction comes to a standstill after one carbonate monolayer has been formed. In case one water monolayer is covering the wollastonite surface, the carbonation is no more barrier-less, yet ending in a localized monolayer. Covered with multilayers of water, the thermodynamic ground state of the wollastonite completely changes due to a metal-proton exchange reaction (MPER, also called early stage hydration) and Ca2+ ions are partially removed from solid phase into the H2O/wollastonite interface. Mobile Ca2+ react again with CO2 and form carbonate complexes, ending in a delocalized layer. By means of high resolution time-of-flight secondary-ion mass-spectroscopy images (ToF-SIMS), we confirm that hydration can lead to a partially delocalization of Ca2+ ions on wollastonite surfaces. Finally, we evaluate the impact of our model surface results by means of Low Energy Ion Scattering (LEIS) spectroscopy combined with careful discussion about the competing reactions of carbonation vs. hydration.

Keywords: Calcium-silicate, carbonation, hydration, metal-proton exchange reaction

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Authors: Lahcen Daoudi, Soukaina Elidrissi, Nathalie Fagel

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The calcareous accumulations in the surface formations of the soil, are a very widespread phenomenon in the arid and semi-arid regions. Many aspects of physical and chemical evolution of these soils were debated for more than one century. The last two decades have witnessed a remarkable interest in the study of the calcrete. In Morocco, as in most Mediterranean countries, soils with carbonate accumulation cover large areas of the territory. The isohumic subtropical soils and red Mediterranean soils include always a horizon of calcrete accumulation. In the lowland of Tensift Al Haouz located in the central part of Morocco, the arable lands are underlain by indurate pedogenic calcrete of various thicknesses; this constitutes a serious handicap for agricultural development in the region. Our aims in this study is to analyze the characteristics of the crusts developed in this area in order to identify the various facies, their geographic distribution and the factors that played a significant role in the differentiation of these calcareous accumulations. The characterizations were based on various techniques including field observations, X-ray diffraction analysis (XRD) for both raw materials and clay fractions, SEM analysis, Calcimetry and Loss On Ignition (LOI). The analysis of encrusting calcrete in a rich and varied observation field as the region of Tensift Al Haouz enabled us to specify the important types of accumulations: diffuse, nodular and massive encrusting. The shape of encrusting as well as their consistency and hardness is clearly related to the contents of CaCO3 of the profiles. Among these facies, the hardpan which results from a complex succession of processes is certainly the most morphologically advanced form of encrusting. The vertical and lateral distribution of these forms in the Tensift Al Haouz area indicates that they do not appear randomly but seem related to well defined environmental conditions. The differentiation and evolution of encrusting is under the influence of two major factors: 1) the availability of carbonate rich solution which is controlled by the topography, the nature and texture of underlying host rock and the detrital processes; 2) the climate which is responsible for the evaporation and crystallization of carbonate.

Keywords: soil calcrete, characterization, morphology, Tensift Al Haouz, Morocco

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Authors: Katarzyna Sobczak

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Over the last few years extensive research on the Lower Palaeozic of the Baltic region has been carried out, associated with growing interest in the unconventional hydrocarbon resources of the area. The present study contributes to this investigation by providing relevant microfacies analysis of Ordovician and Silurian carbonate and clastic deposits of the Polish part of the Baltic Syneclise, using data from the Kętrzyn IG-1, Henrykowo 1 and Babiak 1 boreholes. The analytical data, encompassing sedimentological, palaeontological, and petrographic indicators enables the interpretation of the sedimentary environments and their control factors. The main microfacies types distinguished within the studied interval are: bioclastic wackestone, bioclastic packstone, carbonate-rich mudstone, marlstone, nodular limestone and bituminous claystone. The Ordovician is represented by redeposited carbonate rocks formed in a relatively high-energy environment (middle shelf setting). The Upper Ordovician-Lower Silurian rocks of the studied basin represent sedimentary succession formed during a distinctive marine transgression. Considering the sedimentological and petrological data from the Silurian, a low-energy sedimentary environment (offshore setting) with intermittent high-energy events (tempestites) can be inferred for the sedimentary basin of NE Poland. Slow sedimentation of carbonate ooze and fine-grained siliciclastic rocks, formed under oxygen-deficient conditions of the seabed, favoured organic matter preservation. The presence of the storm beds suggests an episodic nature of seabed oxygenation. A significant part of the analysed depositional successions shows characteristics indicative of deposition from gravity flows, but lacks evidence of its turbidity origins. There is, however, evidence for storms acting as a mechanism of flow activation. The discussed Ordovician-Silurian transition of depositional environments in the Baltic area fits well to the global environmental changes encompassing the Upper Ordovician and the Lower Silurian.

Keywords: Baltic Syneclise, microfacies analysis, Ordovician, Silurian, unconventional hydrocarbons

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Authors: Jackson Andreas Theo Pola, Leksono Mucharam, Hari Oetomo, Budi Susanto, Wisnu Nugraha

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About half of the world oil reserves are located in carbonate reservoirs, where 65% of the total carbonate reservoirs are oil wet and 12% intermediate wet [1]. Oil recovery in oil wet or mixed wet carbonate reservoirs can be increased by dissolving surfactant to injected water to change the rock wettability from oil wet to more water wet. The Wakamuk Field operated by PetroChina International (Bermuda) Ltd. and PT. Pertamina EP in Papua, produces from main reservoir of Miocene Kais Limestone. First production commenced on August, 2004 and the peak field production of 1456 BOPD occurred in August, 2010. It was found that is a complex reservoir system and until 2014 cumulative oil production was 2.07 MMBO, less than 9% of OOIP. This performance is indicative of presence of secondary porosity, other than matrix porosity which is of low average porosity 13% and permeability less than 7 mD. Implementing chemical EOR in this case is the best way to increase oil production. However, the selected chemical must be able to lower the interfacial tension (IFT), reduce oil viscosity, and alter the wettability; thus a special chemical treatment named SeMAR has been proposed. Numerous laboratory tests such as phase behavior test, core compatibility test, mixture viscosity, contact angle measurement, IFT, imbibitions test and core flooding were conducted on Wakamuk field samples. Based on the spontaneous imbibitions results for Wakamuk field core, formulation of SeMAR with compositional S12A gave oil recovery 43.94% at 1wt% concentration and maximum percentage of oil recovery 87.3% at 3wt% concentration respectively. In addition, the results for first scenario of core flooding test gave oil recovery 60.32% at 1 wt% concentration S12A and the second scenario gave 96.78% of oil recovery at concentration 3 wt% respectively. The soaking time of chemicals has a significant effect on the recovery and higher chemical concentrations affect larger areas for wettability and therefore, higher oil recovery. The chemical that gives best overall results from laboratory tests study will also be a consideration for Huff and Puff injections trial (pilot project) for increasing oil recovery from Wakamuk Field

Keywords: Wakamuk field, chemical treatment, oil recovery, viscosity

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Authors: Tomasz Borowski, Dawid Sołoducha, Rafał Rakoczy, Marian Kordas

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The growing interest in magnetic fields applications is visible due to the increased number of articles on this topic published in the last few years. In this study, the influence of various magnetic fields (MF) on the mass transfer process was examined. To carry out the prototype set-up equipped with an MF generator that is able to generate a pulsed magnetic field (PMF), oscillating magnetic field (OMF), rotating magnetic field (RMF) and static magnetic field (SMF) was used. To demonstrate the effect of MF’s on mass transfer, the calcium carbonate precipitation process was selected. To the vessel with attached conductometric probes and placed inside the generator, specific doses of calcium chloride and sodium carbonate were added. Electrical conductivity changes of the mixture inside the vessel were measured over time until equilibrium was established. Measurements were conducted for various MF strengths and concentrations of added chemical compounds. Obtained results were analyzed, which allowed to creation of mathematical correlation models showing the influence of MF’s on the studied process.

Keywords: mass transfer, oscillating magnetic field, rotating magnetic field, static magnetic field

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Authors: Lauren Dawson, Sean Comber, Richard Sandford, Alan Tappin, Bruce Stockley

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The West Dart River is underperforming for Salmon (Salmo salar) survival rates due to acidified pH troughs under the European Water Framework Directive (2000/60/EC). These troughs have been identified as being caused by historic acid rain pollution which is being held in situ by peat bog presence at site and released during flushing events. Natural recovery has been deemed unlikely by the year 2020 using steady state water chemistry models and therefore a program of monitored calcium carbonate (CaCO3) introductions are being conducted to eliminate these troughs, which can drop to pH 2.93 (salmon survival – pH 5.5). The river should be naturally acidic (pH 5.5-6) due to the granite geology of Dartmoor and therefore the CaCO3 introductions are under new methodology (the encasing of the CaCO3 in permeable sacks) to ensure removal should the water pH rise above neutral levels. The water chemistry and ecology are undergoing comprehensive monitoring, including pH and turbidity levels, dissolved organic carbon and aluminum concentration and speciation, while the aquatic biota is being used to assess the potential water chemistry changes. While this project is ongoing, results from the preliminary field trial show only a temporary, localized increase in pH following CaCO3 introductions into the water column. However, changes to the water chemistry have only been identified in the West Dart after methodology adjustments to account for flow rates and spate-dissolution, though no long-term changes have so far been found in the ecology of the river. However, this is not necessarily a negative factor, as the aim of the study is to protect the current ecological communities and the natural pH of the river while remediating only the detrimental pH troughs.

Keywords: anthropogenic acidification recovery, calcium carbonate introductions, ecology monitoring, water chemistry monitoring

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Authors: Sukran Acikel, Mehmet Ekmekci, Otgonbayar Namkhai

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Lignite coal fields in western Turkey generally occurs in tensional Neogene basins bordered by major faults. Karacahisar coal field in Mugla province of western Turkey is a large Neogene basin filled with alternation of silisic and calcerous layers. The basement of the basin is composed of mainly karstified carbonate rocks of Mesozoic and schists of Paleozoic age. The basement rocks are exposed at highlands surrounding the basin. The basin fill deposits forms shallow, low yield and local aquifers whereas karstic carbonate rock masses forms the major aquifer in the region. The karstic aquifer discharges through a spring zone issuing at intersection of two major faults. Municipal water demand in Bodrum city, a touristic attraction area is almost totally supplied by boreholes tapping the karstic aquifer. A well field has been constructed on the eastern edge of the coal basin, which forms a ridge separating two Neogene basins. A major concern was raised about the plausible impact of mining activities on groundwater system in general and on water supply well field in particular. The hydrogeological studies carried out in the area revealed that the coal seam is located below the groundwater level. Mining operations will be affected by groundwater inflow to the pits, which will require dewatering measures. Dewatering activities in mine sites have two-sided effects: a) lowers the groundwater level at and around the pit for a safe and effective mining operation, b) continuous dewatering causes expansion of cone of depression to reach a spring, stream and/or well being utilized by local people, capturing their water. Plausible effect of mining operations on the flow of the spring zone was another issue of concern. Therefore, a detailed representative hydrogeological conceptual model of the site was developed on the basis of available data and field work. According to the hydrogeological conceptual model, dewatering of Neogene layers will not hydraulically affect the water supply wells, however, the ultimate perimeter of the open pit will expand to intersect the well field. According to the conceptual model, the coal seam is separated from the bottom by a thick impervious clay layer sitting on the carbonate basement. Therefore, the hydrostratigraphy does not allow a hydraulic interaction between the mine pit and the karstic carbonate rock aquifer. However, the structural setting in the basin suggests that deep faults intersecting the basement and the Neogene sequence will most probably carry the deep groundwater up to a level above the bottom of the pit. This will require taking necessary measure to lower the piezometric level of the carbonate rock aquifer along the faults. Dewatering the carbonate rock aquifer will reduce the flow to the spring zone. All findings were put together to recommend a strategy for safe and effective mining operation.

Keywords: conceptual model, dewatering, groundwater, mining operation

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Authors: Han Run-Sheng, Li Wen-Yao, Wang Feng, Liu Fei, Qiu Wen-Long, Lei Li

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Accurately positioning detection of concealed deposits or ore-bodies is one of the difficult problems in mineral exploration field. Theory calculation and exploration practices for tunnel gravity indicate that 3D high-precision Tunnel Gravity Exploration Method (TGEM) can find concealed high-density three-dimensional ore-bodies in the depth. The ore-finding breakthroughs at the depth of the Zhaotong Maoping carbonate-hosted Zn–Pb–(Ag–Ge) deposit in Northeastern Yunnan have proved that the exploration method in combination with MEAHFZ method is effective to detect concealed high-density ore-bodies. TGEM may overcome anomalous ambiguity of other geophysical methods for 3D positioning of concealed ore-bodies.

Keywords: 3D tunnel gravity exploration method, concealed high-density Ore-bodies, Zn–Pb–(Ag–Ge) deposit, Zaotong mapping, Northeastern Yunnan

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Authors: A. Thakur, P. S. Panesar, M. S. Saini

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Extraction of lactic acid by emulsion liquid membrane technology (ELM) using n-trioctyl amine (TOA) in n-heptane as carrier within the organic membrane along with sodium carbonate as acceptor phase was optimized by using response surface methodology (RSM). A three level Box-Behnken design was employed for experimental design, analysis of the results and to depict the combined effect of five independent variables, vizlactic acid concentration in aqueous phase (cl), sodium carbonate concentration in stripping phase (cs), carrier concentration in membrane phase (ψ), treat ratio (φ), and batch extraction time (τ) with equal volume of organic and external aqueous phase on lactic acid extraction efficiency. The maximum lactic acid extraction efficiency (ηext) of 98.21%from aqueous phase in a batch reactor using ELM was found at the optimized values for test variables, cl, cs,, ψ, φ and τ as 0.06 [M], 0.18 [M], 4.72 (%,v/v), 1.98 (v/v) and 13.36 min respectively.

Keywords: emulsion liquid membrane, extraction, lactic acid, n-trioctylamine, response surface methodology

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Authors: Tithi Banerjee, Ananya Mukhopadhyay

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The comparison of ancient tidalites recorded in both siliciclastics and carbonates has not been well documented due to a lack of suitable outcropping examples. The Proterozoic Simla Basin, Lesser Himalaya serves a unique example in this regard. An attempt has been made in the present work to differentiate sedimentary facies and architectural elements of tidalites in both siliciclastics and carbonates recorded in the Simla Basin. Lithofacies and microfacies analysis led to identification of 11 lithofacies and 4 architectural elements from the siliciclastics, 6 lithofacies and 3 architectural elements from the carbonates. The most diagnostic features for comparison of the two tidalite systems are sedimentary structures, textures, and architectural elements. The physical features such as flaser-lnticular bedding, mud/silt couplets, tidal rhythmites, tidal bundles, cross stratified successions, tidal bars, tidal channels, microbial structures are common to both the environments. The architecture of these tidalites attests to sedimentation in shallow subtidal to intertidal flat facies, affected by intermittent reworking by open marine waves/storms. The seventeen facies attributes were categorized into two major facies belts (FA1 and FA2). FA1 delineated from the lower part of the Chhaosa Formation (middle part of the Simla Basin) represents a prograding muddy pro-delta deposit whereas FA2 delineated from the upper part of the Basantpur Formation (lower part of the Simla Basin) bears the signature of an inner-mid carbonate ramp deposit. Facies distribution indicates development of highstand systems tract (HST) during sea level still stand related to normal regression. The aggradational to progradational bedsets record the history of slow rise in sea level.

Keywords: proterozoic, Simla Basin, tidalites, inner-mid carbonate ramp, prodelta, TST, HST

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Authors: Hene L. Hapinat, Mae D. Dumapig

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This study aimed to determine the lime potential of 3 mollusks, namely: Crassostrea iredalei (Oyster shell), Turritella terebra (Turret shell), and Anodontia edentula (Mangrove clam shell) as alternative for commercially produced agricultural lime. The hydrogen ion concentration (pH) and the lime concentration using Calcium Carbonate Equivalent (CCE) of each shellfish species were measured and tested for the enhancement of an acidic soil. The experiment was laid out in a Completely Randomized Design (CRD) with 4 treatments replicated 3 times. The treatments were as follows: Treatment A- 100 g agricultural lime; B- 100 g oyster shell lime; C- 100 g turret shell lime; and D- 100 g mangrove clam shell lime. Each treatment was combined to the acidic soil sample. The results were statistically analyzed using One-way Analysis of Variance (ANOVA) and Least Square Difference (LSD) at 0.01 and 0.05 levels of significance. Results revealed that lime produced from the 3 selected mollusks can be a potential source of alternative and/or supplement materials for agricultural lime in dealing with soil acidity, entailing lower cost of farm production.

Keywords: shell lime, pH, calcium carbonate concentrations, mollusks, agricultural lime, lime potential concentration, acidic soil

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Authors: Fatemeh Elmi, Zahra Etemadifar

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Improvement of soil mechanical properties is crucial before its use in construction, as the low mechanical strength and unstable structure of soil in many parts of the world can lead to the destruction of engineering infrastructure, resulting in financial and human losses. Although, conventional methods, such as chemical injection, are often utilized to enhance soil strength and stiffness, they are generally expensive, require heavy machinery, and cause significant environmental effects due to chemical usage, and also disrupt urban infrastructure. Moreover, they are not suitable for treating large volume of soil. Recently, an alternative method to improve various soil properties, including strength, hardness, and permeability, has received much attention: the application of biological methods. One of the most widely used is biocementation, which is based on the microbial precipitation of calcium carbonte crystalls using ureolytic bacteria However, there are still limitations to its large-scale use that need to be resolved before it can be commercialized. These issues have not received enough attention in prior research. One limitation of MICP (microbially induced calcium carbonate precipitation) is that microorganisms cannot operate effectively in harsh and variable environments, unlike the controlled conditions of a laboratory. Another limitation of applying this technique on a large scale is the high cost of producing a substantial amount of bacterial culture and reagents required for soil treatment. Therefore, the purpose of the present study was to investigate soil improvement using the biocementation activity of poly-extremophile, calcium carbonate crystal- producing bacterial strain, Bhargavaea cecembensis N1, in whey as an inexpensive medium. This strain was isolated and molecularly identified from sandy soils in our previous research, and its 16S rRNA gene sequences was deposited in the NCBI Gene Bank with an accession number MK420385. This strain exhibited a high level of urease activity (8.16 U/ml) and produced a large amount of calcium carbonate (4.1 mg/ ml). It was able to improve the soil by increasing the compressive strength up to 205 kPa and reducing permeability by 36%, with 20% of the improvement attributable of calcium carbonate production. This was achieved using this strain in a whey culture medium. This strain can be an eco-friendly and economical alternative to conventional methods in soil stabilization, and other MICP related applications.

Keywords: biocementation, Bhargavaea cecembensis, soil improvement, whey culture medium

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